[go: up one dir, main page]

EP0142045A1 - Sekundärbatterie - Google Patents

Sekundärbatterie Download PDF

Info

Publication number
EP0142045A1
EP0142045A1 EP84112320A EP84112320A EP0142045A1 EP 0142045 A1 EP0142045 A1 EP 0142045A1 EP 84112320 A EP84112320 A EP 84112320A EP 84112320 A EP84112320 A EP 84112320A EP 0142045 A1 EP0142045 A1 EP 0142045A1
Authority
EP
European Patent Office
Prior art keywords
surface area
electrode
negative electrode
secondary battery
positive electrode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP84112320A
Other languages
English (en)
French (fr)
Other versions
EP0142045B1 (de
Inventor
Shigeoki Nishimura
Kazunori Fujita
Hiroyuki Sugimoto
Atsuko Tooyama
Noboru Ebato
Shinpei Matsuda
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hitachi Ltd
Resonac Holdings Corp
Original Assignee
Showa Denko KK
Hitachi Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Showa Denko KK, Hitachi Ltd filed Critical Showa Denko KK
Publication of EP0142045A1 publication Critical patent/EP0142045A1/de
Application granted granted Critical
Publication of EP0142045B1 publication Critical patent/EP0142045B1/de
Expired legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • This invention relates to a secondary battery having a long charge-discharge cycle life.
  • This invention provides a secondary battery comprising a positive electrode, a negative electrode, and an electrolytic solution maintained between the electrodes, at least one of the electrodes being made from a polymer having conjugated double bonds in a main chain, the negative electrode being doped with a cation from the electrolyte, and the positive electrode being doped with an anion from the electrolyte, characterized in that the negative electrode has a larger electrode surface area than the positive electrode.
  • Fig. 1 is a perspective view with partially cross-sectional of a unit cell and Fig. 2 is an enlarged cross-sectional view of the circle A in Fig. 1.
  • Numeral 1 denotes a casing, the outer surface of which is covered by a resin film laminated with a thin film (1 - 100 um) of aluminum, since polyacetylene and doped polyacetylene are unstable for water and oxygen.
  • Numeral 2 is an electrode which is made from, for example, polyacetylene and preferably has therein expanded metal or metal net 3 made of a corrosion-resistant material such as stainless steel, etc., in order to enhance a current collecting effect and to take out an electrode terminal 5.
  • Numeral 4 is a separator in the form of fabric (woven or non-woven fabric) or foam made from a conventional material such as polypropylene, glass fibers, etc., to prevent short circuit between the electrodes and to maintain an electrolytic solution dissolving a dopant. It is possible to stuck a number of such unit cells by using a proper electroconductive separator between unit cells so as to prevent transfer of the electrolytic solution between the unit cells.
  • dopant ions are doped on the electrodes to give a positive electrode and a negative electrode.
  • the negative electrode should have a larger surface area than the positive electrode in order to maintain a balance of the positive and negative electrodes at the time of charge and discharge, and to make a difference in current density at the positive and negative electrodes.
  • a polymer having conjugated double bonds in a main chain for example, polyacetylene [(CH) reduces a resistance value by doping of dopant ions to convert to a metallic state.
  • the electrode since the electrode has a thickness, a distribution of dopant ions is formed at the direction of the electrode thickness, which results in making it impossible to use the whole polyacetylene effectively.
  • the current density is lowered, this tendency can be improved.
  • the electrode area should be made large; this is not suitable for practical use.
  • the difference in diffusion speed of dopant ions due to the difference in current density is remarkable at the negative electrode. Changes of electrode potential at the time of charge and discharge when the current density at the positive and negative electrodes is constant are shown in Fig. 4.
  • Fig. 4 is a graph showing a relationship between the charge rate (%), the discharge rate (%) and the electrode potential E (V vs. Ag/Ag ).
  • Fig. 4 clearly shows that the discharge efficiency of the negative electrode is low. Therefore, it is necessary to lower the current density of only the negative electrode. In order to lower the current density of the negative electrode, it is preferable to make the electrode surface area of the negative electrode larger.
  • electrode surface area includes (a) a geometric opposite surface area (plate height x plate width of an electrode plate opposite to another electrode plate), (b) a gross geometric surface area (plate height x plate width x two surfaces of an electrode plate), (c) a specific surface area per unit weight of electrode active material, and (d) a total specific surface area obtained by multiplying the specific surface area per unit weight by the weight of the electrode active material.
  • the number of charge-discharge cycles increases with an increase of a ratio of the geometric surface area of the negative electrode to the geometric surface area of the positive electrode as shown in Fig. 5.
  • the number of cycles means the number of charge-discharge cycles until the coulombic efficiency becomes lower than 50% at the doping level of 4 mole %.
  • the coulombic efficiency is defined by the following equation:
  • the negative electrode has a geometric surface area preferably 1.03 to 1.20 times (3 to 20% larger) , more preferably 1.05 to 1.1 times (5 to 10% larger) as large as the geometric surface area of the positive electrode.
  • the number of cycles changes with an increase of the specific surface area of negative electrode (e.g. polyacetylene) as shown in Fig. 6.
  • negative electrode e.g. polyacetylene
  • an electrode made from polyacetylene having a specific surface area of 90 m 2 /g is used as the positive electrode and an electrode made from polyacetylene having a specific surface area of 20 to 200 m 2 /g is used as the negative electrode.
  • the specific surface area is measured by a conventional method such as a BET method. As is clear from Fig.
  • the number of cycles maintaining 50% or more of coulombic efficiency at the doping level of 4 mole % is about 50% (a conventional value) when the negative electrode has the specific surface area of about 90 m 2 /g, while the number of cycles of 100 or more can be obtained when the specific surface area is 120 m 2 /g or more e.g. 200 m 2 /g or more. Therefore, it is preferable to use the negative electrode having the specific surface area as large as possible (e.g. 30% or more to 100% larger) compared with the specific surface area of the positive electrode.
  • the number of cycles changes with an increase of a ratio of the doping level of negative electrode to the doping level of positive electrode (in negative value), that is, an increase of the weight of negative electrode (in other words, the total surface area) as shown in Fig. 7.
  • the doping level of negative electrode is lowered and the electrode surface is enlarged, the number of charge-discharge cycles increases.
  • the lowering in the doping level at the negative electrode is preferably 20% or less compared with the doping level of positive electrode. That is, the total specific surface area of the negative electrode is preferably 20% or less and 5% or more larger than that of the positive electrode.
  • polyacetylene As the polymer having conjugated double bonds in a main chain, there can be used polyacetylene, polyphenylene, polythienylene, polypyrrole, polyaniline, and polythiophene alone or as a mixture thereof. Among them, polyparaphenylene, polyaniline and polyacetylene are preferable, and polyacetylene is more preferable.
  • Polyacetylene can be obtained by a conventional process, for example, a process disclosed in J. Polymer Sci, Polymer Chemistry Edition, vol. 12, 11-20 (1974). Such a polymer can be used in the form of fibril.
  • the negative electrode there can be used that made from the polymer having conjugated double bonds in a main chain mentioned above or graphite.
  • the positive electrode can be made from the same or different polymer having conjugated double bonds in a main chain.
  • the negative electrode is formed so as to make the geometric surface area larger than the positive electrode, since the doping of dopant ions to the polyacetylene takes place at the surfaces of polyacetylene fibrils (string-like form of crystalline 0 polyacetylene having a diameter of about 200 A).
  • the negative electrode is made from polyacetylene having a smaller bulk density (that is, having a larger speeific surface area).
  • the negative electrode is made from polyacetylene having a smaller fibril diameter so as to make the specific surface area of the electrode active material larger and to make the current density of the negative electrode substantially smaller than that of the positive electrode.
  • Dopant ions which can be electrochemically doped with the polymer having conjugated double bonds in a main chain such as polyacetylene include:
  • Examples of compounds (dopants) which can provide the dopant anions and dopant cations mentioned above are LiPF 6 , LiBF4, LiClO 4 , NaI, NaClO 4 , KClO 4 , (C 2 H 5 ) 4 NBF 4 , (C 2 H 5 ) 4 NClO 4 , (C 4 H 9 ) 4 NBF 4 , (C 4 H 9 ) 4 NClO 4 , etc. These dopants can be used alone or as a mixture thereof.
  • An electrolytic solution used in this invention is obtained by dissolving the dopant mentioned above in water or non-aqueous solvent.
  • the use of the non-aqueous solvent is preferable for secondary batteries.
  • the non-aqueous solvent are ethers, ketones, nitriles, amines, amides, sulfur compounds, chlorinated hydrocarbons, esters, carbonates, nitro compounds, etc.
  • non-aqueous solvent examples include tetra- hydrafuran, 2-methyltetrahydrofuran, 1,4-dioxane, monoglyme, acetonitrile, propionitrile, 1,2-dichloroethane, y-butyrolactone, dimethoxyethane, methyl formate, propylene carbonate, dimethyl formamide dimethyl sulfoxide, dimethyl thioformamide, sulfolane, etc.
  • solvents can be used alone or as a mixture thereof.
  • the concentration of the electrolytic solution changes depending on the kind of electrolyte (dopant) and solvent, but is usually in the range of 0.001 to 10 mole/liter, more preferably 1 to 5 mol/liter.
  • the electrolytic solution can be impregnated in a separator such as non-woven fabric, etc., which is placed between the two electrodes.
  • the secondary battery according to this invention is well balanced in the positive and negative electrodes at the time of charge and discharge, and the charge-discharge cycle life is remarkably improved.
  • a secondary battery was constructed by using (C 2 H 5 ) 4 NB F 4 as a dopant, CH 3 CN as a solvent in a concentration of 1 mole/liter and electrodes made from polyacetylene.
  • the gross geometric surface area of a negative electrode was made 10% larger than that of a positive electrode.
  • the thickness of the negative electrode was 190 ⁇ m and that of the positive electrode was 200 um.
  • a secondary battery was constructed in the same manner as described in Example 1 except that polyacetylene having the same gross geometric surface area and the same weight was used for forming electrodes but the specific surface area of a negative electrode was made 150 m 2 /g and that of a positive electrode was made 90 m 2 /g.
  • the coulombic efficiency at an initial stage was 99.9%.
  • the charge-discharge cycle properties were measured in the same manner as described in Example 1, the number of charge-discharge cycles maintaining the coulombic efficiency of 50% or more was 153.
  • a secondary battery was constructed in the same manner as described in Example 2 except that the gross geometric surface area of the negative electrode was made 10% larger than that of the positive electrode. The number of charge-discharge cycles maintaining the coulombic efficiency of 50% or more was 164. The cycle life was thus prolonged.
  • a secondary battery was constructed in the same manner as described in Example 1 except that the weight of a negative electrode was made 10% larger than that of a positive electrode. That is, the total specific surface area of the negative electrode was increased in 10%. The number of charge-discharge cycles maintaining the coulombic efficiency of 50% or more was 172.
  • a secondary battery was constructed in the same manner as described in Example 1 except that the weight of a negative electrode was made 50% larger than that of a positive electrode.
  • the number of charge-discharge cycles maintaining the coulombic efficiency of 50% or more was 201.
  • a secondary battery was constructed in the same manner as described in Example 3 except that the weight of a negative electrode was made 10% larger than that of a positive electrode. The number of charge-discharge cycles maintaining the coulombic efficiency of 50% or more was 176.
  • a secondary battery was constructed by using (C 2 H 5 ) 4 NBF 4 as a dopant, CH 3 CN as a solvent in a concentration of 1.0 mole/liter and two electrodes made from polyacetylene and having a thickness of 200 ⁇ m with the same gross geometric surface area.
  • the relationship between the coulombic efficiency and the number of charge-discharge cycles was as shown in Fig. 3.
  • the number of charge-discharge cycles measured in the same manner as described in Example 1 was about 50.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
EP84112320A 1983-10-14 1984-10-12 Sekundärbatterie Expired EP0142045B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP58190980A JPS6084776A (ja) 1983-10-14 1983-10-14 ２次電池
JP190980/83 1983-10-14

Publications (2)

Publication Number Publication Date
EP0142045A1 true EP0142045A1 (de) 1985-05-22
EP0142045B1 EP0142045B1 (de) 1989-02-22

Family

ID=16266861

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84112320A Expired EP0142045B1 (de) 1983-10-14 1984-10-12 Sekundärbatterie

Country Status (5)

Country Link
US (1) US4559284A (de)
EP (1) EP0142045B1 (de)
JP (1) JPS6084776A (de)
CA (1) CA1231754A (de)
DE (1) DE3476843D1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2611405A1 (fr) * 1987-02-25 1988-09-02 Bridgestone Corp Pile electrique a collecteur enrobe

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0183053B1 (de) * 1984-11-29 1990-02-07 VARTA Batterie Aktiengesellschaft Galvanisches Element mit einer Polymerelektrode
DE3506659A1 (de) * 1985-02-26 1986-08-28 Basf Ag, 6700 Ludwigshafen Verbundelektrode
DE3604568A1 (de) * 1986-02-14 1987-08-20 Basf Ag Medium zur irreversiblen informationsspeicherung sowie verfahren zu seiner durchfuehrung
DE3607378A1 (de) * 1986-03-06 1987-09-10 Basf Ag Elektrochemisches sekundaerelement mit mindestens einer polymerelektrode
US4714665A (en) * 1986-12-23 1987-12-22 The Dow Chemical Company Secondary battery
US5714053A (en) * 1995-07-21 1998-02-03 Motorola, Inc. Conducting polymer electrodes for energy storage devices and method of making same
JP4213687B2 (ja) * 2005-07-07 2009-01-21 株式会社東芝 非水電解質電池及び電池パック

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1015915A (en) * 1961-07-05 1966-01-05 Accumulateurs Fixes Improvements in or relating to electrical storage cells
US4321114A (en) * 1980-03-11 1982-03-23 University Patents, Inc. Electrochemical doping of conjugated polymers
US4327157A (en) * 1981-02-20 1982-04-27 The United States Of America As Represented By The Secretary Of The Navy Stabilized nickel-zinc battery
US4442187A (en) * 1980-03-11 1984-04-10 University Patents, Inc. Batteries having conjugated polymer electrodes

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5840781A (ja) * 1981-09-02 1983-03-09 Showa Denko Kk 二次電池

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1015915A (en) * 1961-07-05 1966-01-05 Accumulateurs Fixes Improvements in or relating to electrical storage cells
US4321114A (en) * 1980-03-11 1982-03-23 University Patents, Inc. Electrochemical doping of conjugated polymers
US4442187A (en) * 1980-03-11 1984-04-10 University Patents, Inc. Batteries having conjugated polymer electrodes
US4327157A (en) * 1981-02-20 1982-04-27 The United States Of America As Represented By The Secretary Of The Navy Stabilized nickel-zinc battery

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2611405A1 (fr) * 1987-02-25 1988-09-02 Bridgestone Corp Pile electrique a collecteur enrobe

Also Published As

Publication number Publication date
EP0142045B1 (de) 1989-02-22
JPS6084776A (ja) 1985-05-14
US4559284A (en) 1985-12-17
CA1231754A (en) 1988-01-19
DE3476843D1 (en) 1989-03-30

Similar Documents

Publication Publication Date Title
US4957833A (en) Non-aqueous liquid electrolyte cell
US4463072A (en) Secondary batteries containing room-temperature molten 1,2,3-trialkylimidazolium halide non-aqueous electrolyte
US4804594A (en) Predoped conductive polymers as battery electrode materials
US6787267B2 (en) Electrolyte for electrochemical device
US5442197A (en) Super-capacitor comprising positive and negative electrodes made of a p-doped electron conductive polymer and an electrolyte containing an organic redox compound
CA1149448A (en) Non-aqueous li/mn0.sub.2cell
US4550067A (en) Secondary battery
US4889659A (en) Nitrogenized electronic conductive polymers, their preparation processes, electrochromic display cell and electrochemical generator using these polymers
US4654280A (en) Nonaqueous cell employing a cathode-electrolyte solution containing a boron-containing additive
US4869977A (en) Electrolyte additive for lithium-sulfur dioxide electrochemical cell
EP1205995B1 (de) Sekundärbatterie mit protonenleitendem Polymer
US4886572A (en) Composite electrode comprising a bonded body of aluminum and electroconductive polymer and electric cell using such a composite electrode
EP0165589A2 (de) Sekundärbatterie und Verfahren zu ihrer Herstellung
EP0142045B1 (de) Sekundärbatterie
US6461773B1 (en) Electrolyte for electrochemical device
US4740437A (en) Electrochemical battery having an electrolytically reduced product of a saccharide as the electrode material
DE2557600B2 (de) Galvanisches element mit einem nitril als loesungsmittel fuer das elektrolytsalz
JP2542221B2 (ja) ポリアニリン複合電極を用いた電池
CA1139362A (en) Sulfur trioxide soluble cathode primary cell
JPH0821430B2 (ja) 二次電池
JP2610026B2 (ja) 電池用電極
JP2908794B2 (ja) ポリアニリン電極の使用方法
EP0198484A2 (de) Sekundärbatterie
JP2752377B2 (ja) シート状電極
JPH06275267A (ja) 電極、それを用いた電池およびその製造方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19841220

AK Designated contracting states

Designated state(s): BE CH DE FR GB IT LI NL

17Q First examination report despatched

Effective date: 19860605

R17C First examination report despatched (corrected)

Effective date: 19870511

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE CH DE FR GB IT LI NL

REF Corresponds to:

Ref document number: 3476843

Country of ref document: DE

Date of ref document: 19890330

ET Fr: translation filed
ITF It: translation for a ep patent filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19920814

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19920827

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19921002

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19921031

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19921222

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19921229

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19931012

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19931031

Ref country code: CH

Effective date: 19931031

Ref country code: BE

Effective date: 19931031

BERE Be: lapsed

Owner name: HITACHI LTD

Effective date: 19931031

Owner name: SHOWA DENKO K.K.

Effective date: 19931031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19940501

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19931012

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19940630

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19940701

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST